School of Chemical Engineering

Industrial Catalyst

Abstract
Topic: The catalytic technologies to be introduced in Kazakhstan

Done by: Zhengis Nursultan

Checked by: Sholpan Itkulova

Almaty 2023
 Content
1. Title page………………………………………………………………1
2. Content………………………………………………………………...2
3. Catalytic Technologies for Solving Environmental Problems in the
Production of Fuels and Motor Transport in Kazakhstan……..…..3
4. SCIENTIFIC RESEARCH The KAZNU's students……..………..11
5. CATALYTIC PROCESSING OF YELLOW PHOSPHORUS…...17
6. Reference……………………………………………………………...23
Catalytic Technologies for Solving Environmental Problems in the Production
of Fuels and Motor Transport in Kazakhstan
Abstract: The goal of this research is to clean up the Kazakhstan air basin
by treating toxic exhaust from motor vehicles by altering the hydrocarbon makeup
of motor fuels and removing harmful components from exhaust gases. The
catalytic hydrodearomatization of gasoline fractions (from the reforming stage) of
the Atyrau and Pavlodar Refineries and the neutralization of exhaust gas hazardous
components from an internal combustion engine (ICE) were researched. During
ICE operation, two hydrotreated gasoline fractions were put to the test. The study
demonstrates that Rh-Pt(9:1)/-Al2O3 catalysts exhibit 100% benzene conversion,
which means that benzene is entirely eliminated from both fractions and the
aromatics content drops from 56.24-58.12% to 21.29-21.89%, within the limits of
the Euro-5,6 standard. When fuels are catalytically treated, the ICE engine's fuel
consumption is reduced by 2 to 3% in comparison to the initial gasoline fractions,
and the CO and hydrocarbon contents of the exhaust gases are reduced by 7.8 to
24.7% and 6.6 to 16.2%, respectively. The catalyst 10% Co + 0.5% Pt/Al2O3 was
employed to neutralize the hazardous components in ICE exhaust gas. With this
catalyst, CO conversion is 100% and hydrocarbon conversion is 94.2% and 91.5%
for both gasoline fractions. Electron microscopy (EM), X-ray diffraction (XRD),
Brunauer-Emmett-Teller (BET), thermoprogrammed desorption (TPD), and
thermoprogrammed reduction (TPR) techniques were used to analyze the catalysts.
The TPD and EM methods were used to demonstrate that when Pt is added to the
Rh-catalyst, mixed bimetallic Rh-Pt-agglomerates form, and hydrogen, adsorbed in
the form of a new single peak uncharacteristic of the Rh-catalyst, appears in the
TPD spectrum. As a result, the hydrogenation of benzene and aromatic chemicals
in the gasoline fractions occurs with great activity and selectivity. The creation of
CoAl2O4 spinels, on which inactive oxygen is generated for the oxidation of CO
and hydrocarbons, as demonstrated by the XRD and TPR data. Spinel formation is
prevented when Pt and Mg modify the catalyst, enhancing the catalysts' activity.
Globally, air pollution is primarily caused by transportation by automobile.
Millions of tons of harmful compounds are emitted from exhaust emissions of
vehicles every year. Currently, motor vehicles are responsible for up to 70–80% of
the air pollution in major cities. The yearly harmful emissions from transportation
in Almaty, Kazakhstan, total more than 12 thousand tons of carbon dioxide, around
30 thousand tons of hydrocarbons, and over 150 thousand tons of carbon oxide.
The condensed aromatic chemicals naphthalene, tetralin, and other
monoaromatic and polyaromatic compounds benzene, toluene, and xylene isomers
are examples of aromatic hydrocarbons found in fuels. Given its high volatility,
sluggish engine burn, and high chemical stability in the environment, benzoene is
particularly hazardous. When 1 L of gasoline is consumed, up to 81 g of
benzpyrene (C20H12), a potent carcinogen created during the combustion of
benzene, is produced in the exhaust gases. The amount of nitrogen oxide in the
exhaust gases increases as the amount of aromatic hydrocarbons in the gasoline
increases, as does the combustion temperature [1]. The exhaust emissions from
vehicles account for more than 75% of the benzene in the air [2]. Moreover,
benzene shortens engine life by promoting carbon production in the engine and
increasing the soot composition of exhaust gases [3]. Limiting benzene
concentration in gasoline is required due to its significant carcinogenicity. A
benzene level of less than 1.0% and an aromatic hydrocarbon content of less than
24% are required by Euro standard EURO-5,6. The primary source of benzene in
gasoline is through the reforming process at refineries. Catalytic processes,
specifically the hydrogenation of benzene and aromatic hydrocarbons, are the most
efficient way to alter the chemical structure of these compounds in fuel fractions
and improve the environmental and operational characteristics of motor fuels. The
development of catalytic technology for reducing aromatics in fuel fractions can
enhance the operational properties of gasoline and improve the air quality in
Kazakhstan. With the declining quality of oil and stricter environmental
regulations, catalytic hydrotreating processes are increasingly crucial in oil
refining. Scientists from several countries are working on solving the problem of
hydrodearomatization of refined products. Hydrogenation processes are typically
carried out in the oil refining industry under high temperatures and hydrogen
pressure on metal oxide catalysts that contain transition metals like Co, Mo, Ni,
Cu, and W. Platinum group metal-based catalytic systems, particularly Pt, Pd, Rh,
and Ru, are the most efficient and selective catalysts for hydro-dehydrogenation
reactions. Catalysts based on metals from group VIII and sulphidics are commonly
used in industry. Recently, Pt-Pd catalysts have been widely used for hydrotreating
petroleum products, specifically for reducing benzene in gasoline and aromatics in
diesel fuels, and are closely monitored by researchers. Catalysts reach a uniform
distribution of metals by varying the nature of the support and modifier, which
supports optimum acidity and stability against sulfur-containing compounds. The
combustion of gasoline in vehicle internal combustion engines (ICEs) releases
harmful emissions such as carbon monoxide, unburned light hydrocarbons, soot,
sulfur and nitrogen oxides. Kazakhstan, like many countries, faces air pollution
issues due to the emission of over 4 million tons of harmful gases by
approximately 2 million vehicles every day. The air pollution levels in many
industrial cities of Kazakhstan are 6 to 10 times higher than the established
regulatory limits. Catalytic oxidation of harmful emissions is one of the most
effective methods to neutralize them. Catalytic neutralizers can be divided into
three groups: those with noble metals, transition metal oxides, and mixed catalysts
with d-element oxides and platinum group metals. The most commonly used
catalysts are those with noble metals, despite their high cost. The active
components of catalysts and their mechanism of catalytic reaction have been
studied extensively. Catalytic systems based on cobalt have been shown to have
catalytic activity at low temperatures. The Co3O4/γ-Al2O3 catalyst synthesized by
impregnation methods has high activity. Catalysts obtained by combining Co with
noble metals, such as platinum and Co oxides, have also been investigated, and the
presence of platinum improves catalytic activity and reducibility. Major non-CIS
manufacturers of environmental protection catalysts are constantly improving their
catalysts to comply with stricter environmental protection regulations. The solution
to the environmental problem lies in using environmentally friendly vehicles and
improving gasoline quality, as well as implementing effective systems for
neutralizing exhaust gases. The objective of this study was to examine the catalytic
hydrodearomatization of two gasoline fractions from Kazakhstan refineries to
reduce the content of benzene and aromatics, test hydrotreated fuels in ICEs, and
purify exhaust gases on a metal block-based catalytic neutralizer with a cellular
structure.
The described environmental issue can only be resolved by making vehicles
more ecologically friendly. The quality of gasoline must first be improved, and
then a system must be put in place for effectively neutralizing exhaust gases from
harmful pollutants.
This research aimed to investigate the catalytic hydrodearomatization of two
gasoline fractions from Kazakhstan refineries to lower the content of benzene and
aromatics, test the hydrotreated fuels in ICEs, and investigate the composition (CO
and hydrocarbons) of exhaust gases from the ICEs and purify them on a catalytic
neutralizer based on metal blocks of a cellular structure.
The process of hydrodearomatization was researched using two gasoline
fractions taken from refineries in Kazakhstan in 2020: The stable catalysate of
"Atyrau Refinery" LLP (stable catalysate AR) and the stable catalysate of
"Pavlodar Oil Chemical Refinery" LLP (stable catalysate PR). With 100%
conversion and 100% yield of cyclohexane, bimetallic Rh-Pt(9:1)/-Al2O3 catalysts
produced the best results for benzene hydrogenation.
As part of the hydrogenation process in gasoline fractions, benzene is
converted to cyclohexane, aromatic hydrocarbons to their corresponding
cycloalkanes, and olefinic hydrocarbons to alkanes. Table 1 compares the quantity
of benzene, aromatic hydrocarbons, and olefins in various gasoline fractions to the
Euro-5,6 standard.
Table 1. The content of benzene and aromatic hydrocarbons in gasoline fractions of AR and PR in comparison with Euro-5,6.

Name of the Fraction Benzene Content, Mas. % Aromatics Content, Mas. % Olefin Content, Mas. %
Euro-5,6 <1 24 5
Stable Catalysate AR 4.25 56.24 0.58
Stable Catalysate PR 1.31 58.12 11.02
 Figure 2. Group composition of gasoline fractions over Rh-Pt/γ-Al2O3: (a)
Stable catalysate AR,
(b) stable catalysate PR.

With steady catalysate PR, the situation is similar (Figure 2b): Benzene was
missing, aromatics dropped from 58.12% to 23.82%, olefins from 11.02% to
0.35%, isoparaffins rose from 16.18% to 29.08%, and paraffins grew from 11.25%
to 15.16% as a result of olefin hydrogenation. It should be noted that an increase in
the isostructure's paraffin content suggests both the implementation and
hydroisomerization of hydrogenation reactions.
 The catalysts' surface was investigated using TEM and SEM techniques. The
SEM picture of the Rh-Pt(9:1)/Al2O3 catalyst is depicted in Figure 4. It displays
an adequately uniform surface of the support, on which active metal agglomerates
are discernible. Figure 3b–d displays TEM images of the catalyst with various
amounts of supporting metals. The catalyst Rh-Pt(9:1)/Al2O3 is made up of finely
dispersed particles that range in size from 2 to 25 nm. Additionally, a small amount
of larger, denser particles that are 5 nm in size are present on the surface, and their
microdiffraction patterns show diffuse rings that are related to the metals Pt and Rh
(Figure 3b–d).

Figure 3. Electron microscopy (EM) images of Rh-Pt(9:1)/γ-Al2O3. (a) SEM. (b–d) TEM (an increase of
160,000) at Rh-Pt (9:1) concentration. (a,b) 0.5%. (c) 0.1%. (d) 1.0%.

The study involved testing four types of fuel, namely stable catalysate AR and PR in
their initial state and after undergoing catalytic hydrodearomatization, using a KIPOR
KG160 ICE. The primary objective was to evaluate the toxic components present in the
exhaust emissions of the ICE, including carbon monoxide and hydrocarbons, using an
Optima 7 gas analyzer.

Each type of fuel was filled in the engine's gas tank with 2.5 kg of fuel, and the engine
was run at an average speed of 2500 rpm until the engine stopped or ran out of fuel. The
operation time for each type of fuel was recorded, and the results are presented in Table
5. The results showed that the use of cleaned fuels with lower benzene and aromatic
hydrocarbon content led to a decrease in fuel consumption, as seen from the increase in
the operating time of the ICE by 3% for stable catalysate AR and by 2% for stable
catalysate PR. The engine's operation time was measured from a cold start.
Table 5. Time of internal combustion engine (ICE) operation until complete stop.

Type of Fuel Time, Min.

Initial 92
Stable Catalysate AR
After Experiment 95
Initial 90
Stable Catalysate PR

After Experiment 92

Ten minutes after the start of engine operation at 2500 rpm, the components of
the exhaust gases of the ICE were measured using a gas analyzer. The analysis results
are shown in Table 6.
Table 6. The amount of toxic substances contained in the exhaust gases of the ICE.

Stable Catalysate AR Stable Catalysate PR

Component
Initial After Exp. Initial After Exp.
CO, ppm 8162 7621 9473 7938
CO2, vol. % 11.6 11.0 10.4 11.2
O2, vol. % 3.2 2.9 2.5 2.3
CHx, ppm 1647 1518 2376 1789
SO2, ppm 0 0 0 0
NO, ppm 151 146 180 191
NO2, ppm 4 2 1 5

The findings from the gas analyzer (Table 6) revealed that after catalytic
hydrodearomatization, the amount of carbon monoxide in the stable catalysate AR's
gasoline fraction reduced from 8162 ppm to 7621 ppm (by 6.6%). Hydrocarbon (CHx)
content also dropped from 1647 parts per million to 1518 parts per million (a 7.8%
decrease). Nitrogen oxide levels slightly dropped from 151 to 146 parts per million. The
CO level in the stable catalysate PR dropped from 9473 ppm to 7938 ppm (by 16.2%).
Hydrocarbon concentration dropped by 24.7%, from 2376 ppm to 1789 ppm. It should
be observed that sulfur dioxide is not present in the initial fuels, presumably because
sulfur compounds were completely removed during refinery processing.
The study's next phase involved neutralizing the hazardous byproducts of the
combustion of hydrotreated gasoline fractions in ICEs on a catalytic neutralizer. A
block of platinum-cobalt catalyst was put to the test because early tests on the oxidation
of carbon monoxide revealed that it had the maximum activity. It has been
demonstrated that CO can be entirely eliminated from exhaust gas.
In order to investigate the oxidation of carbon monoxide and hydrocarbons (CHx) in the
make-up of ICE exhaust gases, a catalyst 10%Co + 0.5%Pt/Al2O3 was put in a metal
box in front of the exhaust collector. The outcomes are shown in Table 7.
Table 7. Oxidation of CO and CHx during neutralization of the exhaust gases of an ICE over a 10% Co + 0.5%
Pt/Al2O3 catalyst.

Stable Catalysate AR Stable Catalysate PR

Temperature, ◦C Ppm Conversion (α), % Ppm Conversion (α), %
CO
50 7821 0.0 7938 0.0
100 7054 9.8 7247 8.7
150 3026 61.3 3468 56.3
200 94 98.8 341 95.7
250 0 100 0 100
CHx
50 1518 0 1789 0
100 1433 5.6 1701 4.9
150 776 49.9 953 46.7
200 322 79.8 432 75.8
250 88 94.2 152 91.5

Catalysts Preparation

Pseudoboehmite was converted into the -Al2O3 support for two different
catalyst types (for hydrogenation and neutralization) by calcining it at 650 °C for
two hours. The alumina's specific surface area was 170 m2/g.
The platinum group metals Pt and Rh formed the basis for the catalysts used in this
study. We employed "chemically pure" RhCl33H2O and H2PtCl66H2O to make
the catalysts. Adsorption was used to apply aqueous solutions of H2PtCl6 and
RhCl3 to the ready support -Al2O3. The catalyst samples were removed by
filtering, then dried to a consistent weight at 100 to 110 °C. Supported catalysts
were reduced via electrical heating in a hydrogen stream at 200°C for 4 hours, after
which the catalysts were cooled in a hydrogen stream to ambient temperature. The
produced catalysts were not pyrophoric and were kept over calcium chloride in a
desiccator.
Experiment
In a 0.5 L batch stirred reactor, hydrodearomatization studies were conducted
(Autoclave, from firm Amar Equipments Pvt. Ltd., Mumbai, India.) fitted with a
valve for sampling at various reaction times, as well as an inlet and exhaust valve
for adding or removing gases. The reaction temperature range for hydrogenation
studies was 25–200 °C, while the pressure range was 1.0–5.0 MPa. 200 mL
gasoline fraction and 1 g of catalyst were aggressively mixed to create the reaction
mixture. Prior to conducting each reaction test, the catalyst was initially reduced
using a pure hydrogen flow of 30 mL/min at 200 C (linear heating rate of 7 C
min1) for 2 h. In a stream of hydrogen, the reduced catalyst was cooled to room
temperature before being promptly added to the reaction mixture.
Conclusion
As long as cars burn fuels derived from petroleum, hazardous exhaust gas
emissions will be a problem in terms of air pollution. The issue is getting worse as
a result of the decline in oil quality (heavy, high-sulfur oil), particularly in
Kazakhstan. The fuel's subpar quality causes incomplete combustion and a
significant concentration of hazardous chemicals in vehicle exhaust fumes. The
best ways to address this environmental issue are to develop environmentally
friendly automobiles, enhance the quality of motor fuel, and implement effective
toxic exhaust treatment. Two gasoline fractions from Kazakhstan Refinery
facilities (Atyrau and Pavlodar) were taken (after the reforming stage and without
the additives), and they were hydrodearomatized over Rh-Pt(9:1)/-Al2O3 catalysts.
In order to gauge the volume of hazardous emissions, the hydrotreated fuels
underwent additional testing in an ICE. The work's final phase involved
neutralizing the hazardous chemicals that had developed on metal block
neutralizers. The study's findings demonstrated that benzene-free fuel with a lower
aromatic concentration produces 6.6–24.7% fewer harmful emissions during
combustion compared to the original gasoline fractions, while also removing 100%
of the CO and reducing hydrocarbons by 94% in the exhaust gases. Eliminating
olefins, which make the gasoline unstable, was another good effect. Due to the
hydroisomerization of paraffinic hydrocarbons to isoalkanes during the catalytic
treatment of gasoline fractions, octane levels essentially do not fall. Throughout
the research processes, two efficient catalytic systems were created: 10% Co +
0.5% Pt/Al2O3 supported on metal blocks with a honeycomb structure for
neutralization, and bimetallic catalyst Rh-Pt(9:1)/-Al2O3 for
hydrodearomatization. With up to a 91–100% conversion rate, the catalysts with a
low noble metal content (0.5%) demonstrated remarkable activity. The causes
causing the high activity of the catalysts were discovered by the research of
catalysts using the EM, XRD, BET, TPD, and TPR methodologies. Catalysts might
be suggested for pilot tests on automobiles and at refineries in Kazakhstan with
more study.
SCIENTIFIC RESEARCH The KAZNU's students
For the first time, a composition of low- and high-molecular surfactants is used,
with an eye toward the nature of their interaction on the phase boundary parceling,
to receive direct and revertive emulsions of water with oil and petroleum products.

New approaches to adding depressor chemicals to diesel fuel are being developed.
The overall regularities of well bore colmatation zone development, variables that
speed up or slow down their creation, and the degree of permeability of the well
bore zone in relation to the functional dependency of colmataging elements
passing through them are established.

The newly produced combination, which combines a technological manufacturing

technique with a synthesised product, demonstrated extremely excellent protective
capabilities against steel corrosion in an atmosphere containing hydrogen sulfide.
the slowing down of two conned processes of hydrogen and corrosion pickup is
observed.
It is now possible to receive extremely active and selective bifunctional catalysts
for the isomerization of n-alkanes on the basis of novel ways of receiving fine-
grained nickel with various additions that allow controlling the structural and acid
properties of catalysts. The received catalysts outperform those found in the patent
literature in terms of their characteristics.

For the first time, catalytic systems made of natural materials, such as Kazakhstani
clays and zeolites, have been designed to crack masout with a high degree of
conversion to simple gas oil. In regard to high-sulfur masout, the ideal composite
composition and the activation conditions of the catalysts' active ingredients are
specified.
There are no comparable catalytic systems using natural feedstock for the cracking
process of heavy oil fractions without their initial desulphurization and removal of
bituminous-asphaltenic chemicals.
The first investigation and optimization of the n-paraffine hydrocarbon
isomerization method using modified natural alumosilicates from Kazakhstan. The
composition of n-octane and the Kumkol deposit petroleum straight-run gasoline
conversion products in the presence of natural alumosilicates is demonstrated to be
affected by the nature of modifying additives (Ni, Co, Cr, Fe, and Cu).
For the first time, an effective alkylation catalyst manufacturing method using
modified sulphated zirconia catalysts placed on Al2O3 and natural zeolite is made
available. Alkylation catalyst synthesis value intervals and regeneration essential
parameters are specified.

The Republic of Kazakhstan's brown coals are described in terms of their physical,
chemical, and thermodynamic characteristics, and their suitability for the
hydrogenation process is evaluated.

For the first time, scientific foundations for the development of catalysts for high-
quality two-stage motor fuel derived from the coals of the Karazhyra deposit have
been established. Low pressure was used during the process (3-4 MPa).
The ingredients and method for creating brand-new, superior composite electrodes
for nitrobenzene reduction are specified.

Investigated is the catalytic activity of homogeneous systems based on Pd, Co, Ni,
and Rh phosphinic complexes in the reactions of alcohols and aromatic compounds
carboxylation by the alkaline salts of coal acid monoethers and olefins
carbonylation by carbon oxides.
On the basis of new water-swellable polymers of the glycol vinyl esters acquired
before, numerous polymeric compositions with antiseptics and anesthetics for
treating extensive wounds and burns, as well as the injection form of hydrogel
implant for the contour plastics, were produced. The results of the completed
medical and biological tests indicate that the produced hydrophilous medicine
compositions have a high efficiency. It is demonstrated, in particular, that they
have significant antimicrobic action, actively sorb exudate, do not obstruct oxygen
penetration into a wound, and prevent hypergranulation, which results in the
wound's abstersion and epulosis speeding up. The creation of the medical-technical
guidelines for hydrogel drainages for surgically treating phlegmons and soft-tissue
abscesses in ophthalmology is complete.
It is investigated how copolymers deform under a constant electric field (EF) when
the sample is oriented perpendicular to the direction of the EF. The hypothesis
about the electrostatic nature of the polyampholyte hydrogels deformation under
the influence of electric field is confirmed by the analysis of the influence of
ionogenic groups concentration, рH and ionic strength of the environment, and
electric current density on the size and speed of the deformation. It has been
proven that it can happen in fully ionized gels as well as weakly charged samples.
The presence of an excess of low-molecular ions in a solution relative to gel
concentration is a prerequisite for the occurrence of conversed deformation.
It is suggested that the return deformation mechanism is based on the delayed
diffusion of low-molecular ions that are similarly charged to a polymer.

Depending on the type of ligand groups and characteristics of the external

environment, the polymeric hydrogels that may sorb metal ions in both cationic
and anionic forms are received. The hydrogels based on monoethanolamine vinyl
ester copolymers are known to have a number of benefits over the ion-exchange tar
AM-2B, which has been routinely employed in practice to extract precious metals
from water solutions.
The primary benefit of this is that they may effectively replace the sorbent M-2B in
the technology of precious metals extraction at the gold-mining businesses of the
Republic since they are made using feedstock that is producible in Kazakhstan.
The heap leaching of gold from various industrial and genetic types of ores in the
following deposits: Baktayskoe, Varvarinskoe, Vasil'kovskoe, Dzherek,
Komarovskoe, Maralikha, Mizek, Miyaly, Suzdal'skoe, Akkarginskoe,
Tokhtarovskoe, Elevatornoe is tested using polymeric hydrogels based on the
SVEMEA.
With the use of the M-2B, which eliminates additional costs for the equipment at
the application of the poly-VEMEA, the sorption technology of the industrial gold-
containing solutions processing is carried out on the same installations as
conventionally.
The development of the entire set of project-constructive documentation for the
construction of the coal, gas, oil, and chemical complex is the end result of the
accomplishment of scientific and technical goal programs.
This can lead to the production of surface-active compounds, flotation reagents,
extractants for metallurgy, solvents, sorbents, pharmaceuticals, chemical affinities
for agriculture, monomers for polymers, bituminous mastics, etc.
The first and second stages' technical and economic indicators demonstrate (fig. 1)
that the establishment of petrochemical production at the aforementioned
productivity will have an annual economic impact of 12 million US dollars for coal
and 15 million for petroleum.
It is planned to sell licenses for this technology to companies who are interested.
Large coal-gas-oil-chemical complexes can be built in Kazakhstan using the
country's brown coal reserves, such as those in Karazhyra, Mamyt, Shubarkul,
Kenderlyk, and Kijakty.

Foreign investors are interested in the coal processing work that SRINCT&M is
doing. According to the Contract on Technical Collaboration between the
Scientific Research Institute of New Chemical Technologies and Materials and
Heilongjiang Province Hit Science and Technology Cooperation of China-Russia
Co. Ltd. and the Agreement between the Governments of the Republic of
Kazakhstan and the Government of the Chinese National Republic about Scientific
and Technical Collaboration, the SRINCTM made and launched the explanatory
note of the production project of building the coal-gas-oil-chemical complex with
the productivity of 30000 tons of coal per year, calculations and drafts of the gas-
masout furnace, computer program for the calculation of the atmospheric rectifying
column, drafts of the rectifying column, the full set of drafts of the coal and coal
products, and the pilot stand on coal liquefaction with the productivity of 50 kg of
coal per day. The reactor and associated equipment calculations for the coal
liquefaction block operating at high temperatures and pressure are complete.

Figure 1
The technical and project-constructive specifications for 36 manufacturers are
created using the results of extensive scientific research and project activity. The
technologies that are available for application give a depth of coal and petroleum
refining of at least 90–95%.

Currently, in Aktobe, the National Company "Batys" is working with the Akimat
of the Aktyubinsk region to take the necessary steps to obtain the license for coal
mining and processing as well as the construction of a coal-gas-oil-chemical
complex on the Mamyt coalfield that will produce 100,000 tons of feedstock
annually. The facility will eventually serve as an experimental hub for the
application of cutting-edge techniques in the fields of petrochemistry and deep
processing of hydrocarbon feedstock.
The following is the developed and manufactured basic and auxiliary equipment
for the coal, gas, oil, and chemical complex: two coal liquefaction reactors with
working pressures of 160 atm and 450°C, installation for atmospheric rectification
of coal or crude petroleum, installation for vacuum distillation of heavy gasoil,
installation for catalytic cracking of vacuum distillate, gas-masout furnace for
heating of coal or crude oil, and equipment for briquette production.
The recognized research institute SRINCT&M conducts basic studies in the
following areas that are of particular importance to the republic: processing
hydrocarbonic raw materials; developing new catalysts for various processes;
developing nanostructure polymeric compositions in a variety of directions;
developing the scientific underpinnings of novel technologies of the goods with
increased added value on the basis of physical and chemical processing of coals.
Utilizing the currently widely used resonance-wave processes, which include
vorticose, mechanical, electric, electrochemical, electromagnetic fields, a sound,
ultrasound, radiolysis, plasma, for the mechanochemical activation of reagents for
the processing of coals and their wastes alongside the application of conventional
methods (hydrogenization, hydrogenolysis, gasification, semicoking, and
pyrolysis), is what gives this work its novelty and perspective.
The SRINCT&M is developing technologies and reagents for deodorizing,
dehydrating, desalinating, and desulphurizing hydrocarbons and the byproducts of
their processing, as well as technological models that increase reservoir recovery
and the completeness of petroleum reserves extracted from deposits. It is also
developing the physical and chemical foundations for the production and reception
of a new generation of polyfunctional reagents with complex actions, as well as the
technology for their application.

CATALYTIC PROCESSING OF YELLOW PHOSPHORUS

As the demands for ecological purity and the efficiency of industrial
processes rise, one of the top concerns in the chemistry of phosphorus compounds
and engineering chemistry is the development of "non-chlorine" synthetic methods
of phosphorus derivatives directly from yellow phosphorus. Given that Kazakhstan
is the largest producer of yellow phosphorus in the CIS, this issue is particularly
important to them. One of the main industrial materials, phosphorus has a wide
variety of uses. Derivatives of phosphorus exhibit a wide range of structural and
physical characteristics, and they contribute significantly to important
advancements and interchange.

Yellow phosphorus is created by reducing phosphorites or apatites with coke

at 1300–1500 oC in electric furnaces using silicon dioxide. The USA, Germany,
the Netherlands, and Canada are its top exporting nations for manufacturing.
Nowadays, the globe produces around 1 million tons of phosphorus annually
(excluding the CIS nations). In addition to having the richest deposits of raw
materials containing phosphorus based on the fields of the Karatau basin,
Kazakhstan is one of the five nations with 90% of the world's phosphorus reserves
(South of Kazakhstan). Without production from petrochemistry, Kazakhstan's
chemical industry generates 34,1% of its output through the production of
phosphorics, and the issue of rising phosphoric and phosphorus-containing
production is taken into consideration as one key of Republic economy
The Kazakhstani companies Kazfosfat LLP, Khimprom-2030 LLP, Kazazot LLP,
and JSC are the ones in charge of the phosphoric branch. Each year, reactivated
fosfornye soli businesses generate roughly 100,000 tons of yellow phosphorus,
with 70% of that quantity going to export. From the excavation of phosphate rock
to the manufacturing of phosphorus using electricity and heat, the phosphoric
industry in RK has a complete production cycle. Three phosphoric plants were
built in Kazakhstan in the late 1960s to process the country's richest fields of
phosphorites and coal, and the country rose to third place globally in terms of
output of yellow phosphorus and its derivatives.
These phosphoric enterprises employ a complicated technological system that
starts with the extraction of phosphoric ore, continues with its processing, and ends
with the release and realization of ready raw materials and production for chemical
firms and consumers. 90% of all yellow phosphorus generated is used to produce
phosphorus pentoxide (P2O5) and thermal phosphoric acid, which are both used to
make various phosphoric fertilizers and phosphates. The creation of a significant
amount of toxic waste, including kiln gas, phosphoric slags, and phosphoric slimes
from products, is necessary for the production of yellow phosphorus.
Kiln gas can be used as a technological raw material and in the synthesis of many
different organic compounds due to its high calorific value ( 3000 kcal/m3).
However, kiln gas is not used and is instead burned due to the presence of
undesirable impurities such carbon dioxide, hydrogen, poisonous, fire-dangerous,
and explosive impurities of phosphorus-, sulfur-, and fluorine-containing
compounds. Due to the high proportion of calcium and silicon oxides, electro-
thermo-phosphoric slags, which resemble metallurgical slags in terms of structure,
can be utilized to produce building materials.
The classic method of making organophosphorus compounds involves first
oxidizing yellow phosphorus with chlorine, followed by the phosphorylation of an
organic substrate with phosphorus chlorides (PCl3, PCl5) and oxychlorides
(POCl3). During the multistage commercial process, a significant amount of
hydrogen chloride is released, leading to increased costs for its neutralization, a
decrease in the yield of products containing phosphorus, as well as substantial
environmental issues.

The contemporary chemistry of phosphorus can be likened to the chemistry of

carbon in terms of contemporary accomplishments and scientific aspirations.
Yellow phosphorus, which is readily available and relatively inexpensive, serves as
a raw material for the commercial synthesis of valuable acids of phosphorus and
the esters based on them (P4).
Research teams in Russia, Germany, Italy, France, and the United States are
currently working to create the fundamental underpinnings of such procedures,
according to an analysis of scientific and patent literature. They employ a variety
of techniques, including the use of transitional metal complexes as platforms for
the activation and transformation of the P4 tetrahedral molecule, chemical and
electrochemical methods, as well as techniques that have an external impact on the
phosphorus molecule, such as X-ray processing, mechanical processing, or
ultrasonic processing. Despite yellow phosphorus's significant accomplishments in
coordination chemistry, research on catalytic processes involving it is far less
extensive.
The oxidizing reaction of P4 by oxygen with formation of trialkylphosphates in
alcohol-arene solutions of copper(II) chloride was the first instance of a metal
complex catalyzing yellow phosphorus organic reactions. Professor Dorfman
Ya.A. and coworkers made this discovery in the homogeneous catalysis lab of the
D.V. Sokolsky Institute of organic catalysis and electrochemistry (IOCE, Almaty).
They conducted an organized study of the procedures for the catalytic
functionalization of yellow phosphorus based on the interactions of elemental
phosphorus with water, alcohols, amines, and phenol in the presence of oxidizers
like oxygen, peroxide compounds, water, and the various polar and non-polar
solvents accelerated by individual and mixed catalysts based on transitional metal
complexes.
For many years, researchers at the D.V. Sokolsky IOCE laboratory for
homogeneous catalysis have worked to develop the theoretical and practical
aspects of reactions involving low-valence phosphorus compounds as well as
catalytic methods for converting yellow phosphorus and wasting its production
into valuable inorganic and organic compounds. The catalytic technique for
extracting pure carbon dioxide and ammonia from kiln gas of phosphoric synthesis
was tried in 1991 at Jambyl JSC Khimprom. An alkaline solution was used to
remove impurities from compounds containing fluorine and sulfur, while a copper-
ammonia solution catalyzed the oxidation of phosphorus and phosphine to
inorganic phosphates.
In a laboratory, a new catalytic method for producing organophosphorus chemicals
from waste phosphoric acid and elemental phosphorus is devised. The use of
catalysts enables the oxidizing phosphorylation of an organic substrate to be
completed in one step while using not only yellow phosphorus but also phosphides
of the transitional metals and hydrogen, polymeric red phosphorus,
hypophosphites, and arene extracts of underdeveloped phosphoric slimes.
Production of phosphorus compounds is substantially more environmentally safe
after yellow phosphorus is removed from the commercial cycle. Esters of
phosphoric acid are produced when aliphatic alcohols C1 to C5 are used as organic
substrates in a catalytic process with good yield and selectivity.
Trialkylphosphates are priceless organophosphorus compounds that are widely
employed as softeners, lubrication additives, fire retardants, and extragents
required for the intricate processing of rare, noble, and radioactive metal ores. The
integrated bench testing of an organophosphorus chemical synthesis method using
alcohols and yellow phosphorus as the catalyst made it possible to provide the
process flow diagram and conduct pilot tests on the D.V. Sokolsky IOCE trial
base. During testing, it was demonstrated that tributylphosphate could be produced
safely by direct catalytic synthesis from P4 and butanol under mild circumstances
using conventional chemical processing equipment.
Research of low-valence phosphorus compound oxidizing P-O coupling with
alcohol provide the scientific foundation for the creation of novel catalytic
procedures for extracting important element-organic compounds directly from
phosphoric industry products.
The Laboratory of Homogeneous Catalysis in Kazakhstan has been conducting
basic research programs in the field of catalytic reactions since 1997. These
programs are aimed at creating new high technologies for the production of
organophosphorus derivatives from phosphorus, phosphides, alcohols, olefins, and
other organic compounds. The research projects conducted by the laboratory
include state-registered programs such as "New catalytic reactions with
participation of phosphine, phosphorus, alcohols, olefins and other organic
compounds as a basis of creation of new high technologies" (0197PK00487, 1997-
1999), "Ecologically safe catalytic syntheses of the organophosphorus derivatives
from compounds of elemental and low-valence phosphorus" (0100PK00100, 2000-
2002), "Theoretical bases of catalytic processes of organophosphorus compounds
obtaining from phosphorus and phosphides" (0103PK00320, 2003-2005),
"Scientific bases of eco-efficient catalytic syntheses of the element organic
compounds from sulfur, derivatives of phosphorus and alcohols" (0106PK00452,
2006-2008), and "Creation of scientific bases of ecologically optimized catalytic
processes of organic phosphates and phosphites obtaining from yellow
phosphorus" (0109PK00442, 2009-2011). These programs aim to develop new
methods and theoretical bases for the synthesis of organophosphorus compounds
with an emphasis on environmentally friendly processes.
In the past 20 to 30 years, phosphorus chemistry has advanced dramatically.
Numerous new reactions have been discovered as a result of the lengthy search for
high-performance synthetic processes for phosphorus compounds that has been
going on in numerous scientific hubs around the globe. Regularities of phosphorus'
chemical behavior in relation to reagents of various kinds have also been
established. The most significant advancement in the field of coordination of
transitional metal complexes was made in the area of activation techniques for
yellow phosphorus. Data from scientific studies on the coordination chemistry of
yellow phosphorus and P4 reactions with nucleophilic and electrophilic reagents
under chemical, electrochemical, and catalytic activation are published in the
world's scientific literature.
There is now a lack of high-quality and diversified phosphorus-containing
manufacturing in the modern phosphoric sector. Although yellow phosphorus is
produced in Kazakhstan by extracting phosphate rock and arranging for its
manufacture, there is no direct manufacturing of phosphorus acids and esters from
P4. The creation of alternative "non-chlorine" processes for the direct synthesis of
phosphorus inorganic and organic compounds from yellow phosphorus is a crucial
task that will enable the solution of economic issues in the mining, petrochemical,
and agricultural sectors as well as environmental issues brought on by the
continuous escalation of environmental protection regulations. Yet, questions
persist regarding P4's role in organic reaction catalysis and the catalytic chemistry
of yellow phosphorus in general.
A number of well-known scientific institutions, including the A.E. Arbuzov
Institute of Organic and Physical Chemistry of the KazanSC of RAS (Sinyashin
O.G., Budnikova Yu.G.), the A.E. Favorskii Irkutsk Institute of Organic Chemistry
of the Siberian Branch of the Russian Academy of Science (Trofimov B.A.,
Gusarova N.K.), the Institute of Inorganic Chemistry, have been conducting
(Cummins C.C.).
Despite notable advancements in the field of coordination chemistry, the oxidizing
inorganic and organic reactions of P4 in the catalytic mode, to the description of
their kinetics and the mechanism, identification of the nature of catalytically active
intermediates, and chemical and electrochemical transformations of the molecule
P4 in the presence of various nucleophilic and electrophilic reagents, still receive
little attention.
Scientists from the Kazakh National University's al-Farabi are currently working
on a topic involving the search for alternative "non-chlorine" methods of
converting yellow phosphorus into useful phosphorus compounds. Their work was
done in accordance with fundamental and applied research programs between 2015
and 2017 at the Center for Physico-Chemical Methods of Research and Analysis
for Organic Chemistry and the Research Institute of New Chemical Technologies
and Materials on the project 3662/GF4 "Development of catalytic processes of
oxidation and hydrogenation for the organic compounds obtaining from yellow
phosphorus, alcohols, and unsaturated hydrocarbons" (No. state registration
0115PK01013) (No. state registration 0115PK00515).
President N.A. Nazarbaev assigned the task of developing export-focused
productions, joint ventures in the fields of oil and gas and transportation
mechanical engineering, metallurgy, chemistry, and agrarian sector in order to
qualify Kazakhstan as one of the most developed countries with a robust economy.
Strengthening the competitive positions of the chemical industry on the domestic
and international markets by utilizing the scientific and technical capabilities of the
branch would serve as the primary objective of Kazakhstan's long-term and steady
growth. The chemical industry will reach new heights thanks to the enhancement
of consumer qualities in socially conscious production and the range extension of
available resources.
Reference:
Massenova, Alma & Kalykberdiyev, Maxat & Sass, Alexandr & Kenzin, Nail &
Ussenov, Abzal & Baiken, Amankeldi & Rakhmetova, Kenzhegul. (2020).
Catalytic Technologies for Solving Environmental Problems in the Production of
Fuels and Motor Transport in Kazakhstan. Catalysts. 10. 1197. Doi:
10.3390/catal10101197.
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